Computational Studies on the Platinum(II)-Catalyzed Cycloisomerization of 1,6-Dienes into Bicyclopropanes: A Mechanistic Quandary Evaluated by DFT

被引：6
|
作者：
Bell, Franziska [1 ]
Holland, Jason [1 ]
Green, Jennifer C. [1 ]
Gagne, Michel R. [2 ]
机构：
[1] Univ Oxford, Inorgan Chem Lab, Oxford OX1 3QR, England
[2] Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 USA
来源：
ORGANOMETALLICS | 2009年 / 28卷 / 07期
关键词：
CYCLOPROPANE FORMATION; PSEUDOPOTENTIAL CALCULATIONS; ELECTROPHILIC ACTIVATION; CATALYZED CYCLIZATION; CARBENE COMPLEXES; ENZYME MECHANISMS; INTERNAL OLEFINS; AB-INITIO; GOLD; BIOSYNTHESIS;
D O I：
10.1021/om800760x
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The mechanism of the (bis(phosphanylethyl)phosphane)Pt2+-catalyzed cycloisomerization reaction of 7-methylocta-1,6-diene to form 1-isopropylbicyclo[3.1.0]hexane was studied using computational methods. The cyclopropanation step was found to be the turnover-limiting step. The overall reaction proceeds via both a 5-exo and a 6-endo route. W conformations were shown to facilitate cyclopropanation, but do not have any influence on the rate of the 1,2-hydride shifts.
引用
收藏
页码：2038 / 2045
页数：8
相关论文
共 20 条
  • [1] Nickel(II)-Catalyzed Cycloisomerization of 1,6-Dienes
    Du, Zhongjian
    Ji, Chenlei
    Wang, Xu
    Zhang, Sijian
    Wang, Zhenyu
    You, Yang'en
    SYNTHESIS-STUTTGART, 2025, 57 (07): : 1306 - 1312
  • [2] Stereoselective nickel-catalyzed cycloisomerization of 1,6-dienes
    Boeing, Christian
    Hahne, Julia
    Francio, Giancarlo
    Leitner, Walter
    ADVANCED SYNTHESIS & CATALYSIS, 2008, 350 (7-8) : 1073 - 1080
  • [3] Development, synthetic scope, and mechanistic studies of the palladium-catalyzed cycloisomerization of functionalized 1,6-dienes in the presence of silane
    Kisanga, P
    Widenhoefer, RA
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (41) : 10017 - 10026
  • [4] Development, synthetic scope, and mechanistic studies of the palladium-catalyzed cycloisomerization of functionalized 1,6-dienes in the presence of silane
    Kisanga, Philip
    Widenhoefer, Ross A.
    1600, ACS, Washington, DC, USA (122):
  • [5] Cycloisomerization of functionalized 1,5-and 1,6-dienes catalyzed by cationic palladium phenanthroline complexes
    Kisanga, P
    Goj, LA
    Widenhoefer, RA
    JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (02): : 635 - 637
  • [6] Silane-promoted cycloisomerization of functionalized 1,6-dienes catalyzed by a cationic (π-allyl)palladium complex
    Widenhoefer, RA
    Perch, NS
    ORGANIC LETTERS, 1999, 1 (07) : 1103 - 1105
  • [7] Triarylphosphine Ligands with Hemilabile Alkoxy Groups: Ligands for Nickel(II)-Catalyzed Olefin Dimerization Reactions. Hydrovinylation of Vinylarenes, 1,3-Dienes, and Cycloisomerization of 1,6-Dienes
    Biswas, Souvagya
    Zhang, Aibin
    Raya, Balaram
    RajanBabu, T. V.
    ADVANCED SYNTHESIS & CATALYSIS, 2014, 356 (10) : 2281 - 2292
  • [8] Synthetic and mechanistic studies of the cycloisomerization and cyclization/hydrosilylation of functionalized dienes catalyzed by cationic palladium(II) complexes
    Widenhoefer, RA
    ACCOUNTS OF CHEMICAL RESEARCH, 2002, 35 (10) : 905 - 913
  • [9] Rhodium(III)-Catalyzed Asymmetric Borylative Cyclization of Cyclohexadienone-Containing 1,6-Dienes: An Experimental and DFT Study
    Tan, Yun-Xuan
    Zhan, Fang
    Xie, Pei-Pei
    Zhang, Shuo-Qing
    Wang, Yi-Fan
    Li, Qing-Hua
    Tian, Ping
    Hong, Xin
    Lin, Guo-Qiang
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2019, 141 (32) : 12770 - 12779
  • [10] PALLADIUM-CATALYZED AND RHODIUM-CATALYZED CYCLIZATION OF 1,6-DIENES, 1,7-DIENES AND 1,8-DIENES TO CYCLOPENTENES AND METHYLENECYCLOPENTENES - CRYSTAL-STRUCTURE OF DICHLORO(4,4-DIACETYLHEPTA-1,6-DIENE)PLATINUM(II)
    GRIGG, R
    MALONE, JF
    MITCHELL, TRB
    RAMASUBBU, A
    SCOTT, RM
    JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1984, (08): : 1745 - 1754
12